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Kinetics and Mechanisms

Review Question:
What feature(s) of the plot of concentration of A vs. time given below clearly indicates that the
reaction is first-order and not second-order with respect to A?

[A] vs. time

2

1.75

1.5

1.25

1
[A]

0.75

0.5

0.25

0
0 50 100 150 200 250
time (s)

Model 1: A Theory of Reaction Rates

A simple model has been proposed that attempts to explain the large variation in the observed
rates of chemical reactions. This collision theory of reaction rates provides a basis for
understanding why some chemical reactions are fast and others are slow:
 Molecules must collide in order for reactions to occur.
 The rate at which molecules collide (the collision frequency) is generally greater than the
rate of reactions involving those molecules. This suggests that not all collisions between
molecules are effective in producing a reaction.
 There is, therefore, a minimum energy of collision required for a reaction to occur. This is
related to the fact that in order for the reaction to proceed, bonds must be broken. The
state of the reacting system in which the molecules are colliding, and in which bonds are
being broken (and new bonds are being formed) is known as the transition state, or the
activated complex. The minimum energy needed to form this transition state is the
activation energy, Ea.
The energetics of a reaction are often depicted by a diagram showing how the energy (enthalpy) of
the molecules changes as the reaction proceeds; this is referred to as a reaction coordinate
diagram. An example of such a diagram is shown below for the reaction ONBr(g) + ONBr(g) 
2NO(g) + Br2(g)
ON—Br—Br –NO

ONBr + ONBr
H
NO + NO + Br2

reaction coordinate

Figure 1: Enthalpy vs. Reaction coordinate for a typical reaction

The reaction coordinate is a measure of the progress of a reaction. It represents all the changes that
must occur in the course of the reaction, including the bending, breaking, and making of bonds.

Questions
1. Which is more likely to weaken or break the bond between the nitrogen atom and the bromine
atom in ONBr: a violent collision between two ONBr molecules, or a gentle collision? Explain
your reasoning.

2. Is a violent collision between two ONBr molecules more likely to occur at a high temperature or
at a low temperature? Explain your answer based on molecular-level reasoning.

3. If two ONBr molecules collide as diagrammed below, is the collision likely to lead to two NO
molecules and one Br2 molecule? ________

O—N—Br   O—N—Br

Propose (by drawing) a more effective collision between these two molecules:
4. In Model 1, the collision theory suggests that not all collisions between molecules are effective
in causing a reaction.
a. Provide one reason why all collisions between molecules might not be effective in
causing a reaction:

b. Provide a second reason:

c. What could be done to the reaction conditions to overcome the limitation in a)?

d. What could be done to the reaction conditions to overcome the limitation in b)?

5. On Figure 1, draw a vertical line or bracket that indicates the magnitude of the enthalpy change
∆H for the reaction.
a. Is ∆H positive or negative? __________________
b. Is the reaction in Figure 1 endothermic or exothermic? Explain your reasoning.

6. Circle the activated complex (or transition state) in Figure 1.

7. Indicate on Figure 1 the magnitude of Ea for the forward reaction:

ONBr(g) + ONBr(g)  2NO(g) + Br2(g)

8. Indicate on Figure 1 the magnitude of Ea for the reverse reaction

2NO(g) + Br2(g)  ONBr(g) + ONBr(g)

9. What is the mathematical relationship between Ea(forward), Ea(reverse), and ∆H?

Application Questions
1. Construct a reaction coordinate diagram (similar to Figure 1) for a typical endothermic
reaction.

Which has the larger activation energy, the forward or reverse reaction?

2. The reaction O3(g) + NO(g)  O2(g) + NO2(g) has Ea = 10.7 kJ/mol and ∆H = -199.8 kJ/mol.
What is the activation energy for the following reaction?
O2(g) + NO2(g)  O3(g) + NO(g)

3. The reaction H2O + H+  H3O+ has a very small activation energy for the forward reaction.
Draw the Lewis structure for H2O and give two reasons why the activation energy is small.

4. Why is the activation energy for the forward reaction of the following reaction very large?
N2(g) + 3 H2(g)  2 NH3(g)
Exercises:
1. Indicate the molecularity (unimolecular, bimolecular, or termolecular) of each of the following
elementary steps. Give the rate law for each step, which for elementary steps only, the rate
order depends on the stoichiometry of the elementary step. The first two are shown as an
example.
a. O3  O2 + O Unimolecular Rate = k[O3]
b. ONBr + ONBr  NO + NO + Br2 Bimolecular Rate = k[ONBr]2
c. N2O2  NO + NO
d. NO + NO  N2 + O2
e. I(g) + H2(g)  HI(g) + H(g)

2. The following reaction is experimentally determined to be first order with respect to NO 2 and
F2:
2 NO2(g) + F2(g)  2 NO2F (g) rate = k[NO2][F2]
In order for a mechanism to be valid, the rate law for the slowest step in the mechanism must
make the experimentally determined rate law for the overall reaction. The rate law given above
is consistent with which of the following mechanisms?
a. NO2 + F2  NO2F + F fast
NO2 + F  NO2F slow

b. NO2 + F2  NO2F + F slow

NO2 + F  NO2F fast

c. F2  F + F slow
2 NO2 + 2 F  2 NO2F fast

3. Add the molecular species for the two steps in each of the mechanisms in 2.
a. How is this sum related to the stoichiometry of the overall reaction?

b. How valid would a mechanism be if the elementary steps did not add up to the overall
reaction?
 4. Consider the following reaction:
2 NO2(g) + O3(g)  N2O5(g) + O2(g)
Several experiments were performed at 298 K beginning with only NO2 and O3. The results are
shown in the table below:
[NO2] [O3] Initial rate of
reaction (M/sec)
0.50 1.00 2.5x104
2.00 1.00 1.0x105
2.00 2.00 2.0x105

a. Determine the order with respect to each reactant.

b. Write the rate law for the reaction, including the value of the rate constant, k, with units.

c. Construct the best reaction coordinate diagram that you can for this reaction.
Δ H =−198 kJ /mole
i. Make sure that your diagram accounts for the fast rate of reaction shown in the
data above

d. Determine whether or not the proposed reaction mechanism is consistent with the rate
law that you determined above. Explain your reasoning.
NO2 + O3  NO3 + O2 slow
NO3 + O2  NO2 + O3 fast
NO3 + NO2  N2O5 fast

This activity has been modified from one that originally appeared in Moog, R.S. and John Farrell, Chemistry: A Guided Inquiry, 3rd ed. 2006.